Cooling liquid composition for fuel cell

ABSTRACT

A coolant composition for a fuel cell unit, which contains at least one aliphatic alcohol having unsaturated bonds in the molecules having 2 to 20 carbon atoms each. The coolant composition maintains the electrical conductivity of the coolant at 10 μS/cm or below as well as the fluctuation of the electrical conductivity within the range of 0 to 10 μS/cm.

RELATED APPLICATION

This application is a continuation of PCT Application No. PCT/JP2003/016646 filed Dec. 24, 2003 which claims priority to PCT Application No. PCT/JP2003/008879 filed Jul. 11, 2003, each of which are hereby incorporated by references herein.

TECHNICAL FIELD

The present invention relates to a coolant composition for fuel cells, and specifically to such a coolant composition for automobiles. In particular, the present invention relates to a coolant composition that provides an excellent antifreeze property and is capable of maintaining the electrical conductivity of the coolant adequately low for a long period of time.

BACKGROUND TECHNOLOGY

Generally a fuel cell unit which generates electrical power is provided as a stack of a plurality of fuel cells. During power generation, heat is generated from the fuel cells. To cool the fuel cell unit, a cooling plate is inserted between every few fuel cells.

A fluid path for coolant is provided in each cooling plate in order to cool the fuel cell unit.

A coolant for a fuel cell unit circulates within the stack of the fuel cells and cools the fuel cells. If the electrical conductivity of the coolant is “high”, the electricity generated in the fuel cells partially flows into the coolant, resulting in loss of electrical power generated in the fuel cell unit.

Conventionally, pure water which is very low in electrical conductivity and thus high in electrical insulation has been used as coolant for fuel cell units.

In the case of a fuel cell system which is used intermittently, such as a fuel cell system for an automobile, the temperature of the coolant is subject to the atmospheric temperature when not in use. When the atmospheric temperature falls below the freezing point, pure water coolant would freeze, potentially leading to physically damaging the cooling plates. The battery performance of the fuel cell system would then deteriorate.

Accordingly, low electrical conductivity and good antifreeze property are required of coolant for fuel cell systems, especially for fuel cell systems of automobiles.

A coolant composition containing a base component of a water-glycol blend and an amine based alkaline additive that works to maintain the electrical conductivity of the coolant low has been proposed (see Japanese Unexamined Patent Publication 2001-164244).

Such a glycol may be oxidized during use, and may produce ionic substances. Such ionic substances raise electrical conductivity of the coolant.

The coolant paths of a fuel cell system are generally provided with an ion exchanger or ion exchange resin to remove such ionic substances.

However, the capacity of the ion exchanger deteriorates as time goes by because the ion exchanger is “consumed” for removal of the ionic substances.

Accordingly, it is an object of the present invention to provide an anti-freeze coolant composition for a fuel cell unit, which is capable of maintaining the electrical conductivity of a coolant low for a long period of time by suppressing generation of ionic substances in the coolant.

DISCLOSURE OF THE INVENTION

In the following, a coolant composition for fuel cells according to the present invention is described in detail. The coolant composition of the present invention is characterized by containing at least one aliphatic alcohol having unsaturated bonds in the molecules thereof. The base component of this coolant composition possesses low electrical conductivity and antifreeze properties. Preferably, the base component contains at least one ingredient selected from the group consisting of water, glycols, saturated alcohols and glycol ethers.

The glycols may be ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol and hexylene glycol.

The saturated alcohols may be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol.

The glycol ethers may be alkyl ether of polyoxy alkylene glycol, such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether.

The aliphatic alcohols possess unsaturated bonds in the molecules, and maintain electrical conductivity low. The electrical conductivity of the coolant according to the present invention is maintained at 10 μS/cm or below, and the fluctuation in electrical conductivity of the coolant during a long use is maintained within the range from 0 μS/cm to 10 μS/cm.

The aliphatic alcohols of the present invention are not easily removed by the ion exchanger used in the cooling system and are capable of keeping the electrical conductivity of the coolant low for a long time. As they are not removed by the ion exchanger, the expected function of the aliphatic alcohols according to the present invention will last long without losing ion exchanging capability.

Preferably, the aliphatic alcohols have 2 to 20 carbon atoms per molecule. The aliphatic alcohols may be selected from allyl alcohol, 2-butene-1-ol, 3-butene-1-ol, 1-butene-3-ol, 2-methyl-2-propene-1-ol, 4-pentene-1-ol, 1-pentene-3-ol, 2-pentene-1-ol, 2-methyl-3-butene-2-ol, 3-methyl-2-butene-1-ol, 3-methyl-3-butene-1-ol, 2-hexene-1-ol, 3-hexene-1-ol, 4-hexene-1-ol, 5-hexene-1-ol, 1-hexene-3-ol, 6-heptene-1-ol, 2-heptene-1-ol, 4-heptene-1-ol, 7-octene-1-ol, 2-octene-1-ol, 3-octene-1-ol, 5-octene-1-ol, 3-octene-2-ol, 1-octene-3-ol, 2-nonene-1-ol, 3-nonene-1-ol, 6-nonene-1-ol, 8-nonene-1-ol, 1-nonene-3-ol, 2-decene-1-ol, 4-decene-1-ol, 9-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 2-undecene-1-ol, 10-undecence-1-ol, 2-dodecene-1-ol, 2-propyne-1-ol, 2-butyne-1-ol, 1-butyne-3-ol, 3-butyne-1-ol, 1-pentyne-3-ol, 2-pentyne-1-ol, 3-pentyne-1-ol, 4-pentyne-1-ol, 4-pentyne-2-ol, 3-methyl-1-butyne-3-ol, 1-hexyne-3-ol, 3-hexyne-1-ol, 5-hexyne-3-ol, 2-hexyne-1-ol, 5-hexyne-1-ol, 3-methyl-1-pentyne-3-ol, 2-cyclohexene-1-ol, 2,4-hexadiene-1-ol, 1-heptyne-3-ol, 2-heptyne-1-ol, 3-heptyne-1-ol, 4-heptyne-2-ol, 5-heptyne-3-ol, 5-methyl-1-hexyne-3-ol, 3,4-dimethyl-1-pentyne-3-ol, 3-ethyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-octyne-1-ol, 1-octyne-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptyne-3-ol, 3-ethyl-1-heptyne-3-ol, 3-nonyne-1-ol, 2,6-nonadiene-1-ol, 3,6-nonadiene-1-ol, 1-cyclohexyl-2-butene-1-ol, 2-decyne-1-ol, 3-decyne-1-ol, 2,4-decadiene-1-ol, 4-ethyl-1-octyne-3-ol, 3,7-dimethyl-2,6-octadiene-1-ol, 10-undecyne-1-ol, 2,4-undecadiene-1-ol, 2,4-dodecadiene-1-ol, 3-methyl-1-pentene-4-yn-3-ol, 1-ethynyl-1-cyclohexanol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 3-butene-1,2-diol, 2-methylene-1,3-propanediol, 7-octene-1,2-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3-pentene-2-ol, 4-pentene-2-ol, 2-methyl-3-butene-1-ol, 5-hexene-2-ol, 3-methyl-1-pentene-3-ol, 4-methyl-3-pentene-1-ol, 4-methyl-2-cyclohexene-1-ol, 5-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 1,4-pentadiene-3-ol, 1,5-hexadiene-3-ol, 1,6-heptadiene-4-ol, 2-methyl-3-hexyne-2-ol, 1-ethynyl-1-cyclopentanol, 10-undecyne-1-ol, 1,5-hexadiene-3,4-diol, and 3,5-cyclohexadiene-1,2-diol.

Desirably, the aliphatic alcohols are contained within the range from 0.01 part by weight to 15 parts by weight against 100 parts by weight of the base component. Outside of this range, satisfactory results will not be attained or waste will result.

The coolant composition of the present invention may additionally contain an antifoaming agent, coloring agent, etc. A conventionally known rust inhibitor, such as molybdate, tungstate, sulfate, nitrate and/or benzoate may also be added in an amount that does not increase the electrical conductivity of the coolant of the present invention.

EMBODIMENTS AND COMPARISONS

The coolant composition of the present invention is described hereunder using embodiments of the present invention. Table 1 shows the respective components of Embodiments 1 to 3 of the present invention and Comparisons 1 to 3. Embodiment 1 consisted of ethylene glycol, 3-butene-1-ol (aliphatic unsaturated alcohol), and deionized water. Embodiment 2 consisted of ethylene glycol, 4-pentene-1-ol (aliphatic unsaturated alcohol), and deionized water. Embodiment 3 consisted of ethylene glycol, 2,5-dimethyl-3-hexyne-2,5-diol (aliphatic unsaturated alcohol), and deionized water. Comparison 1 consisted of ethylene glycol and deionized water. Comparison 2 consisted of ethylene glycol, 1-butanol (aliphatic saturated alcohol), and ion exchanged water. Comparison 3 consisted of ethylene glycol, 1-pentanol (aliphatic saturated alcohol), and dedionized water. TABLE 1 (parts by weight) Com- Com- Com- Embod- Embod- Embod- par- par- par- Item iment 1 iment 2 iment 3 ison 1 ison 2 ison 3 ethylene glycol 50 50 50 50 50 50 water 50 50 50 50 50 50 3-butene-1-ol   0.5 — — — — — 4-pentene-1-ol —   0.5 — — — — 1-butanol — — — —   0.5 — 1-pentanol — — — — —   0.5 2,5- — —   0.5 — — — dimethyl-3- hexyne- 2,5-diol

The electrical conductivity after oxidation treatment of each embodiment and comparison was measured. The results are shown in Table 2. The oxidation treatment of each sample was performed over 168 hours at 100° C. TABLE 2 Com- Com- Com- Embod- Embod- Embod- par- par- par- Item iment 1 iment 2 iment 3 ison 1 ison 2 ison 3 Initial 0.2 0.2 0.2 0.2 0.2 0.3 conductivity (μS/cm) Post oxidation 9.5 4.4 2.9 42.6 43.9 39.6 conductivity (μS/cm)

As Table 2 shows, Embodiments 1 to 3 and Comparisons 1 to 3 each had an initial electrical conductivity 0.3 μS/cm or below, while each of the electrical conductivities of Comparisons 1 to 3 after oxidation was much higher (42.6 for Comparison 1, 43.9 for Comparison 2, and 39.6 for Comparison 3). In contrast, the electrical conductivities of Embodiments 1 to 3 after oxidation all remained within the range from 0 μS/cm to 9.5 μS/cm (9.5 for Embodiment 1, 4.4 for Embodiment 2, and 2.9 for Embodiment 3).

Effects of the Invention

The aliphatic alcohol having unsaturated bonds in the molecules contained in the coolant composition of the present invention prevents generation of ionic substances as a result of oxidation of the base component of the coolant otherwise and is capable of maintaining the electrical conductivity of the coolant low for a long period of time. In addition, as the aliphatic alcohol in the coolant composition of the present invention is not easily removed by an ion exchanger in cooling systems, the duration of effectiveness of the ion exchanger is extended. 

1. A coolant composition for a fuel cell unit, comprising a fuel cell unit coolant comprising at least one aliphatic alcohol that comprises an unsaturated bond.
 2. The coolant composition according to claim 1, wherein a number of carbon atoms per molecule of said at least one aliphatic alcohol is 2 to
 20. 3. The coolant composition according to claim 2, wherein said at least one aliphatic alcohol is selected from the group consisting of allyl alcohol,2-butene-1-ol, 3-butene-1-ol, 1-butene-3-ol, 2-methyl-2-propene-1-ol, 4-pentene-1-ol, 1-pentene-3-ol, 2-pentene-1-ol, 2-methyl-3-butene-2-ol, 3-methyl-2-butene-1-ol, 3-methyl-3-butene-1-ol, 2-hexene-1-ol, 3-hexene-1-ol, 4-hexene-1-ol, 5-hexene-1-ol, 1-hexene-3-ol, 6-heptene-1-ol, 2-heptene-1-ol, 4-heptene-1-ol, 7-octene-1-ol, 2-octene-1-ol, 3-octene-1-ol, 5-octene-1-ol, 3-octene-2-ol, 1-octene-3-ol, 2-nonene-1-ol, 3-nonene-1-ol, 6-nonene-1-ol, 8-nonene-1-ol, 1-nonene-3-ol, 2-decene-1-ol, 4-decene-1-ol, 9-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 2-undecene-1-ol, 10-undecence-1-ol, 2-dodecene-1-ol, 2-propyne-1-ol, 2-butyne-1-ol, 1-butyne-3-ol, 3-butyne-1-ol, 1-pentyne-3-ol, 2-pentyne-1-ol, 3-pentyne-1-ol, 4-pentyne-1-ol, 4-pentyne-2-ol, 3-methyl-1-butyne-3-ol, 1-hexyne-3-ol, 3-hexyne-1-ol, 5-hexyne-3-ol, 2-hexyne-1-ol, 5-hexyne-1-ol, 3-methyl-1-pentyne-3-ol, 2-cyclohexene-1-ol, 2,4-hexadiene-1-ol, 1-heptyne-3-ol, 2-heptyne-1-ol, 3-heptyne-1-ol, 4-heptyne-2-ol, 5-heptyne-3-ol, 5-methyl-1-hexyne-3-ol, 3,4-dimethyl-1-pentyne-3-ol, 3-ethyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-octyne-1-ol, 1-octyne-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptyne-3-ol, 3-ethyl-1-heptyne-3-ol, 3-nonyne-1-ol, 2,6-nonadiene-1-ol, 3,6-nonadiene-1-ol, 1-cyclohexyl-2-butene-1-ol, 2-decyne-1-ol, 3-decyne-1-ol, 2,4-decadiene-1-ol, 4-ethyl-1-octyne-3-ol, 3,7-dimethyl-2,6-octadiene-1-ol, 10-undecyne-1-ol, 2,4-undecadiene-1-ol, 2,4-dodecadiene-1-ol, 3-methyl-1-pentene-4-yn-3-ol, 1-ethynyl-1-cyclohexanol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 3-butene-1,2-diol, 2-methylene-1,3-propanediol, 7-octene-1,2-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3-pentene-2-ol, 4-pentene-2-ol, 2-methyl-3-butene-1-ol, 5-hexene-2-ol, 3-methyl-1-pentene-3-ol, 4-methyl-3-pentene-1-ol, 4-methyl-2-cyclohexene-1-ol, 5-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 1,4-pentadiene-3-ol, 1,5-hexadiene-3-ol, 1,6-heptadiene-4-ol, 2-methyl-3-hexyne-2-ol, 1-ethynyl-1-cyclopentanol, 10-undecyne-1-ol, 1,5-hexadiene-3,4-diol, 3,5-cyclohexadiene-1,2-diol, and combinations thereof.
 4. The coolant composition according to claim 1, wherein the coolant further comprises a base component selected from the group consisting of water, glycols, saturated alcohols, glycol ethers, and combinations thereof.
 5. The coolant composition according to claim 1, wherein the coolant comprises from 0.01 part by weight to 15 parts by weight of said at least one aliphatic alcohol relative to 100 parts by weight of a base component.
 6. The coolant composition according to claim 1, wherein said at least one aliphatic alcohol maintains electrical conductivity of the coolant at 10 μS/cm or below.
 7. The coolant composition of claim 1, wherein said at least one aliphatic alcohol maintains fluctuations in electrical conductivity of the coolant within the range from 0 μS/cm to 10 μS/cm.
 8. A method of cooling a fuel cell unit comprising a cooling system, the method comprising adding the composition of claim 1 to a fuel cell cooling system.
 9. A method of making a fuel cell unit coolant composition comprising mixing a base component with at least one aliphatic alcohol comprising an unsaturated bond.
 10. The method of claim 9 wherein the base component comprises water, glycol, saturated alcohol, glycol ether, or a combination thereof.
 11. The method of claim 9 wherein the coolant composition comprises from 0.01 part by weight to 15 parts by weight of the aliphatic alcohol relative to 100 parts by weight of the base component.
 12. The method of claim 9 wherein the aliphatic alcohol maintains the electrical conductivity of the coolant composition at 10 μS/cm or below.
 13. The method of claim 9 wherein the aliphatic alcohol maintains fluctuations in electrical conductivity of the coolant composition within the range from 0 μS/cm to 10 μS/cm.
 14. A fuel cell unit comprising a fuel cell coolant system configured to circulate coolant within a fuel cell stack to cool fuel cells in the stack, with the coolant comprising at least one aliphatic alcohol that comprises an unsaturated bond.
 15. The fuel cell unit of claim 14 wherein a number of carbon atoms per molecule of said at least one aliphatic alcohol is 2 to
 20. 16. The fuel cell unit of claim 14 wherein said at least one aliphatic alcohol is selected from the group consisting of allyl alcohol,2-butene-1-ol, 3-butene-1-ol, 1-butene-3-ol, 2-methyl-2-propene-1-ol, 4-pentene-1-ol, 1-pentene-3-ol, 2-pentene-1-ol, 2-methyl-3-butene-2-ol, 3-methyl-2-butene-1-ol, 3-methyl-3-butene-1-ol, 2-hexene-1-ol, 3-hexene-1-ol, 4-hexene-1-ol, 5-hexene-1-ol, 1-hexene-3-ol, 6-heptene-1-ol, 2-heptene-1-ol, 4-heptene-1-ol, 7-octene-1-ol, 2-octene-1-ol, 3-octene-1-ol, 5-octene-1-ol, 3-octene-2-ol, 1-octene-3-ol, 2-nonene-1-ol, 3-nonene-1-ol, 6-nonene-1-ol, 8-nonene-1-ol, 1-nonene-3-ol, 2-decene-1-ol, 4-decene-1-ol, 9-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 2-undecene-1-ol, 10-undecence-1-ol, 2-dodecene-1-ol, 2-propyne-1-ol, 2-butyne-1-ol, 1-butyne-3-ol, 3-butyne-1-ol, 1-pentyne-3-ol, 2-pentyne-1-ol, 3-pentyne-1-ol, 4-pentyne-1-ol, 4-pentyne-2-ol, 3-methyl-1-butyne-3-ol, 1-hexyne-3-ol, 3-hexyne-1-ol, 5-hexyne-3-ol, 2-hexyne-1-ol, 5-hexyne-1-ol, 3-methyl-1-pentyne-3-ol, 2-cyclohexene-1-ol, 2,4-hexadiene-1-ol, 1-heptyne-3-ol, 2-heptyne-1-ol, 3-heptyne-1-ol, 4-heptyne-2-ol, 5-heptyne-3-ol, 5-methyl-1-hexyne-3-ol, 3,4-dimethyl-1-pentyne-3-ol, 3-ethyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-octyne-1-ol, 1-octyne-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptyne-3-ol, 3-ethyl-1-heptyne-3-ol, 3-nonyne-1-ol, 2,6-nonadiene-1-ol, 3,6-nonadiene-1-ol, 1-cyclohexyl-2-butene-1-ol, 2-decyne-1-ol, 3-decyne-1-ol, 2,4-decadiene-1-ol, 4-ethyl-1-octyne-3-ol, 3,7-dimethyl-2,6-octadiene-1-ol, 10-undecyne-1-ol, 2,4-undecadiene-1-ol, 2,4-dodecadiene-1-ol, 3-methyl-1-pentene-4-yn-3-ol, 1-ethynyl-1-cyclohexanol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 3-butene-1,2-diol, 2-methylene-1,3-propanediol, 7-octene-1,2-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3-pentene-2-ol, 4-pentene-2-ol, 2-methyl-3-butene-1-ol, 5-hexene-2-ol, 3-methyl-1-pentene-3-ol, 4-methyl-3-pentene-1-ol, 4-methyl-2-cyclohexene-1-ol, 5-decene-1-ol, 3,7-dimethyl-6-octene-3-ol, 1,4-pentadiene-3-ol, 1,5-hexadiene-3-ol, 1,6-heptadiene-4-ol, 2-methyl-3-hexyne-2-ol, 1-ethynyl-1-cyclopentanol, 10-undecyne-1-ol, 1,5-hexadiene-3,4-diol, 3,5-cyclohexadiene-1,2-diol, and combinations thereof.
 17. The fuel cell unit of claim 14 wherein the coolant further comprises a base component selected from the group consisting of water, glycols, saturated alcohols, glycol ethers, and combinations thereof.
 18. The fuel cell unit of claim 14 wherein the coolant comprises from 0.01 part by weight to 15 parts by weight of said at least one aliphatic alcohol relative to 100 parts by weight of a base component.
 19. The fuel cell unit of claim 14 wherein post oxidation electrical conductivity of the coolant is about 10 μS/cm or below.
 20. The fuel cell unit of claim 14 wherein electrical conductivity fluctuations between initial conductivity of the coolant and post oxidation conductivity of the coolant range from 0 μS/cm to 10 μS/cm. 